Ligand-induced substrate steering and reshaping of [Ag2(H)]+ scaffold for selective CO2 extrusion from formic acid

Athanasios Zavras, George N. Khairallah, Marjan Krstić, Marion Girod, Steven Daly, Rodolphe Antoine, Philippe Maitre, Roger J. Mulder, Stefanie-Ann Alexander, Vlasta Bonačić-Koutecký (), Philippe Dugourd () and Richard A. J. O’Hair ()
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Athanasios Zavras: School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne
George N. Khairallah: School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne
Marjan Krstić: Center of Excellence for Science and Technology – Integration of Mediterranean region (STIM) at Interdisciplinary Center for Advanced Science and Technology (ICAST), University of Split
Marion Girod: Institut des Sciences Analytiques, Université de Lyon, Université Lyon 1-CNRS-ENS Lyon
Steven Daly: Institut Lumière Matière, Université Lyon 1-CNRS, Université de Lyon
Rodolphe Antoine: Institut Lumière Matière, Université Lyon 1-CNRS, Université de Lyon
Philippe Maitre: Laboratoire de Chimie Physique, Bâtiment 349, Université Paris-Sud, CNRS, Université Paris-Saclay
Roger J. Mulder: CSIRO Manufacturing
Stefanie-Ann Alexander: School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne
Vlasta Bonačić-Koutecký: Center of Excellence for Science and Technology – Integration of Mediterranean region (STIM) at Interdisciplinary Center for Advanced Science and Technology (ICAST), University of Split
Philippe Dugourd: Institut Lumière Matière, Université Lyon 1-CNRS, Université de Lyon
Richard A. J. O’Hair: School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne

Nature Communications, 2016, vol. 7, issue 1, 1-8

Abstract: Abstract Metalloenzymes preorganize the reaction environment to steer substrate(s) along the required reaction coordinate. Here, we show that phosphine ligands selectively facilitate protonation of binuclear silver hydride cations, [LAg2(H)]+ by optimizing the geometry of the active site. This is a key step in the selective, catalysed extrusion of carbon dioxide from formic acid, HO2CH, with important applications (for example, hydrogen storage). Gas-phase ion-molecule reactions, collision-induced dissociation (CID), infrared and ultraviolet action spectroscopy and computational chemistry link structure to reactivity and mechanism. [Ag2(H)]+ and [Ph3PAg2(H)]+ react with formic acid yielding Lewis adducts, while [(Ph3P)2Ag2(H)]+ is unreactive. Using bis(diphenylphosphino)methane (dppm) reshapes the geometry of the binuclear Ag2(H)+ scaffold, triggering reactivity towards formic acid, to produce [dppmAg2(O2CH)]+ and H2. Decarboxylation of [dppmAg2(O2CH)]+ via CID regenerates [dppmAg2(H)]+. These gas-phase insights inspired variable temperature NMR studies that show CO2 and H2 production at 70 °C from solutions containing dppm, AgBF4, NaO2CH and HO2CH.

Date: 2016
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DOI: 10.1038/ncomms11746

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